Highly functional epoxidized resins and coatings

ABSTRACT

The invention provides highly functional epoxy resins that may be used themselves in coating formulations and applications but which may be further functionalized via ring-opening reactions of the epoxy groups yielding derivative resins with other useful functionalities. The highly functional epoxy resins are synthesized from the epoxidation of vegetable or seed oil esters of polyols having 4 or more hydroxyl groups/molecule. In one embodiment, the polyol is sucrose and the vegetable or seed oil is selected from corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof. Methods of making of the epoxy resin and each of its derivative resins are disclosed as are coating compositions and coated objects using each of the resins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to PCT International Application No.PCT/US2011/023753, filed Feb. 4, 2011; which claims priority to U.S.Application 61/302,124, filed Feb. 6, 2010; U.S. Application 61/355,453,filed Jun. 16, 2010; U.S. Application 61/355,487, filed Jun. 16, 2010;and U.S. Application 61/435,338, filed Jan. 23, 2011; each of which isincorporated herein by reference.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with government support under grant no.2007-38202-18597 awarded by the US Department of Agriculture (USDA). TheUS Government has certain rights in the invention.

BACKGROUND

The utilization of renewable raw materials has been considered as one ofthe “green chemistry” approaches that can contribute to sustainabledevelopment. Metzger, et al., C. R. Chim., 2004, 7, 569. Plant oils,naturally occurring triglycerides of fatty acids, make up the greatestproportion of the current consumption of renewable feedstocks used toprepare biobased polymers. Meier, et al., Chem. Soc. Rev., 2007, 36,1788; Baumann, et al., Angew. Chem. Int. Ed. Engl. 1998, 27, 41;Biermann, et al., Angew. Chem. Int. Ed., 2000, 39, 2206; Khot, et al.,J. Appl. Polym. Sci., 2001, 82, 703. Carbohydrates are another importantclass of renewable sources of green materials, and the versatileindustrial work of transforming low molecular weight carbohydrates (e.g.mono- and di-saccharides) into products as the potential to replacepetrochemical products is very attractive. F. W. Lichtenthaler and S.Peters, C. R. Chim., 2004, 7, 65-90.

Cationic UV curable coatings account for only about 8% of all theUV-coatings used in industry (Gu, et al., J. Coat. Technol. 2002, 74,49.) primarily due to fewer types of cationic polymerizable monomers andoligomers available in the market (Zou, et al., Macromol. Chem. Phys.2005, 206, 967). The three major types of epoxides used aresilicon-containing epoxides, epoxidized seed oils (soybean or linseedoils) and cycloaliphatics. The seed oil epoxides are synthesized fromrenewable natural resources. A factor that prevents the extensive use ofepoxidized oils is the relative low reactivity of the internal epoxygroups (Zou, et al., Macromol. Chem. Phys. 2005, 206, 967 andSangermano, et al., J. Mater. Sci. 2002, 37, 4753). There remains,however, a need to explore new processes to broaden the applications ofthe seed oil epoxides. In recent years there has been growing interestin using vegetable oils as raw materials in resin production.

Vegetable oils are derived from the seeds of various plants and arechemically triglycerides of fatty acids. That is, vegetable oils consistof three moles of fatty acids esterified with one mole of glycerol. Asshown below in Formula I, fatty acids are linear carboxylic acids having4 to 28 carbons and may be saturated or ethylenically unsaturated.

Different plants produce oils having differing compositions in the fattyacid portion of the oil. Naturally-occurring vegetable oils are bydefinition mixtures of compounds, as are the fatty acids comprisingthem. They are usually either defined by their source (soybean, linseed)or by their fatty acid composition. A primary variable thatdifferentiates one vegetable oil from another is the number of doublebonds in the fatty acid; however, additional functional groups can bepresent such as hydroxyl groups in castor oil and epoxide groups invernonia oil. Table 1 below identifies the typical fatty acidcomposition for some commonly occurring vegetable oils.

TABLE 1 Fatty Acid Unsaturation Coconut Corn Soybean Safflower SunflowerLinseed Castor Tall Oil FA Tung C₁₂ Lauric 0 44 C₁₄ Myristic 0 18 C₁₆Palmitic 0 11 13 11 8 11 6 2 5 4 C₁₈ Stearic 0 6 4 4 3 6 4 1 3 1 Oleic 17 29 25 13 29 22 7 46 8 Ricinoleic 1 87 Linoleic 2 2 54 51 75 52 16 3 414 Linolenic 3 9 1 2 52 3 3 Eleaosteric 3 80 Iodine 7.5- 103- 120- 140-125- 155- 81- 165- 160- Value 10.5 128 141 150 136 205 91 170 175

Vegetable oils have been used extensively as binder systems in paintsand coatings for centuries. Drying oils, such as linseed oil, have beenused as a component of paint binders since drying oils can be convertedinto a tack free film upon reaction with atmospheric oxygen in a processcalled autoxidation. Vegetable oils have also been used in the synthesisof alkyd resins by combining the fatty acids in the oils with othermonomers to form a fatty acid containing polyester resin. Vegetable oilsalso have several advantages of being renewable, biodegradable and hencehave less impact on the environment. Vegetable oils can impart desirableflexibility and toughness to the otherwise brittle cycloaliphaticepoxide system. Wan Rosli, et al., Eur. Polym. J. 2003, 39, 593.

Sucrose, β-D-fructofuranosyl-α-D-glucopyranoside, is a disaccharidehaving eight hydroxyl groups. The combination of sucrose and vegetableoil fatty acids to yield sucrose esters of fatty acids (SEFA) as coatingvehicles was first explored in the 1960s. Bobalek, et al., OfficialDigest, 1961, 453; Walsh, et al., Div. Org. Coatings Plastic Chem.,1961, 21, 125. However, in these early studies, the maximum degree ofsubstitution (DS) was limited to about 7 of the available 8 hydroxylgroups. The resins do not appear to have been commercialized at thattime. In the early 2000s, Proctor & Gamble (P&G) Chemicals developed anefficient process for industrially manufacturing SEFAs commerciallyunder the brand name SEFOSE with a high DS of at least 7.7 (representinga mixture of sucrose hexa, hepta, and octaesters, with a minimum of 70%by weight octaester) (U.S. Pat. Nos. 6,995,232; 6,620,952; and6,887,947), and introduced them with a focus on marketing to thelubricant and paint industries. Due to their low viscosities (300-400mPa·s), SEFOSE sucrose esters can be used as binders and reactivediluents for air-drying high solids coatings. Formula II displays thepossible molecular structure of a sucrose ester with full substitution.Procter and Gamble has reported a process to prepare highly substitutedvegetable oil esters of sucrose using transesterification of sucrosewith the methyl esters of sucrose. U.S. Pat. No. 6,995,232.

An epoxide group is a three-membered, cyclic ether containing two carbonatoms and one oxygen atom. An epoxide can also be called an oxirane. Asin known in the art, an epoxy group has the structure shown in formulaIll in which R and R′ are organic moieties representing the remainder ofthe compound.

Epoxy resins are materials consisting of one or more epoxide groups. Dueto the strained nature of the oxirane ring, epoxide groups are highlyreactive and can be reacted with nucleophiles such as amines, alcohols,carboxylic acids. Thus, epoxy resins having two or more epoxy groups canbe reacted with compounds having multiple nucleophilic groups to formhighly crosslinked thermoset polymers. Oxiranes can also behomopolymerized. Epoxy resins having two or more epoxy groups can behomopolymerized to form highly crosslinked networks. Crosslinked epoxyresins are used in a large number of applications including coatings,adhesives, and composites, among others. The most commonly used epoxyresins are those made from reacting bisphenol-A with epichlorohydrin toyield difunctional epoxy resins.

Epoxidation is one of the most important and useful modifications usingthe double bonds of ethylenically unsaturated fatty compounds (Scheme 1below), since epoxide is a reactive intermediate to readily generate newfunctional groups. Ring-opening of epoxide via nucleophilic additionleads to a large number of products, such as diol, alkoxy alcohol (etheralcohol), hydroxy ester (ester alcohol), amino alcohol, and others.Through epoxide opening of epoxidized soybean oil using alcohols,triglyceride polyols intended for application in polyurethanes have beensuccessfully prepared by Petrovic and co-works. U.S. Pat. Nos. 6,107,433and 6,6867,435; and Zlatanić, et al., J. Polym. Sci., Part B: Polym.Phys., 2004, 42, 809.

Epoxide reaction with ethylenically unsaturated acids has been widelyutilized to synthesize oil-based free-radical UV-curable coating resinsby reacting acrylic acids with epoxidized vegetable oils (EVOs).LaScala, et al., J. Am. Oil Chem. Soc., 2002, 79, 59; LaScala, et al.,Polymer, 2005, 46, 61; and Pelletier, et al. J. Appl. Polym. Sci., 2006,99, 3218.

Epoxide groups, or oxirane groups, as discussed, can be synthesized bythe oxidation of vinyl groups. Findley, et al., (JACS, 67, 412-414(1945)) reported a method to convert the ethylenically unsaturatedgroups of triglyceride vegetable oils to epoxy groups, as shown in thescheme below. A number of other processes and catalysts have beendeveloped to also achieve epoxidized oils in good yields.

Generally, while there are four techniques that can be employed toproduce epoxides from olefinic molecules (Mungroo, et al., J. Am. OilChem. Soc., 2008, 85, 887), the in situ performic/peracetic acid (HCOOHor CH₃COOH) process appears to be the most widely applied method toepoxidize fatty compounds. Scheme 2 displays the reaction mechanism,which consists of a first step of peroxyacid formation and a second stepof double bond epoxidation. Recently, the kinetics of epoxidation ofvegetable oils and the extent of side reactions was studied using anacidic ion exchange resin as catalyst and revealed that the reactionswere first order with respect to the amount of double bonds and thatside reactions were highly suppressed; the conversion of double bonds toepoxides was also high. Petrović, et al., Eur. J. Lipid Sci. Technol.,2002, 104, 293; and Goud, et al., Chem. Eng. Sci., 2007, 62, 4065. Thecatalyst, Amberlite IR 120, is an acidic ion exchange resin, a copolymerbased on styrene (98 wt %) crosslinked by divinylbenzene (2 wt %). Itsacidity is generated by sulfonic acid groups attached to the polymerskeleton.

Epoxides generated from the epoxidation of double bonds of ethylenicallyunsaturated fatty acids are known as internal epoxides—both carbons ofthe heterocyclic ring are substituted with another carbon. The mostcommonly used epoxy resins are the bisphenol-A diglycidyl ether resins.The epoxy groups on these resins are of the type known as externalepoxides—three of the four substituent groups on the heterocyclic ringare hydrogen atoms. Since internal epoxides are much less reactive thanexternal epoxides in most epoxy curing reactions, the rolestraditionally assigned to epoxidized oils are as stabilizers andplasticizers for halogen-containing polymers (i.e. poly(vinyl chloride))(Karmalm, et al., Polym. Degrad. Stab., 2009, 94, 2275; Fenollar, etal., Eur. Polym. J., 2009, 45, 2674; and Bueno-Ferrer, et al., Polym.Degrad. Stab., 2010, 95, 2207), and reactive toughening agents for rigidthermosetting plastics (e.g. phenolic resins). Miyagawa, et al., Polym.Eng. Sci., 2005, 45, 487. It has also been shown that EVOs can be curedusing cationic photopolymerization of epoxides to form coatings.Crivello, et al., Chem. Mater., 1992, 4, 692; Thames, et al., Surf.Coat. Technol., 1999, 115, 208; and Ortiz, et al., Polymer, 2005, 46,1535.

Crivello reported the preparation of a number of epoxidized vegetableoils and their crosslinking using cationic photoinitiators. U.S. Pat.No. 5,318,808; Crivello, et al., Chem. Mater., 1992, 4, 692-699. Ingeneral, the coatings formed from photopolymerization were soft due tothe low crosslink density obtained and the flexible aliphatic nature ofthe backbone of the vegetable oils. Epoxy-anhydride curing usingepoxidized soybean oil (ESO) and dicarboxylic acid anhydrides in thepresence of tertiary amine and imidazole as catalysts have also beenstudied (Rösch et al., Polymer Bulletin, 1993, 31, 679-685; Annelise, etal., Journal of the American Oil Chemists' Society, 2002, 79, 797-802)but there remains a need for improved epoxy-anhydride curingcompositions.

The radiation curing industry has been using acrylated resins as the keycomponents in coatings and inks. Bajpai, et al., Pigment & ResinTechnology 2004, 33, 160. Acrylated soybean oils (ASO) takes up 90% ofacrylated resin's market consumption due to its low cost andavailability. Prantil, B. Journal of Oil and Colour Chemist'sAssociation 2000, 83, 460. ASO resin is great for printing ink due toits excellent pigment wetting power. Bajpai, et al., Pigment & ResinTechnology 2004, 33, 160. Furthermore, the acrylate groups in themolecules are able to participate in free-radical polymerization in thecoating system. Bunker, et al., Journal of Polymer Science: Part A:Polymer Chemistry 2002, 40, 451-458. A need still remains for improvedacrylated resins, particularly resins which can be derived from low-costand renewable raw materials.

SUMMARY OF THE INVENTION

It has been found that by increasing the functionality of epoxy groups(number of epoxy groups per molecule) using vegetable oil basedcompounds, the problems of soft crosslinked coatings can be overcome.The invention provides highly functional epoxy resins that may be usedthemselves in coating formulations and applications but which may befurther functionalized via the epoxy groups yielding derivative resinswith other useful functionalities.

Highly functional epoxy resins are synthesized from the epoxidation ofvegetable or seed oil esters of polyols having 4 or more hydroxylgroups/molecule. The epoxy resins can be cured using UV photoinitiatorsto hard coatings. The novel epoxy resins can also be incorporated intoformulations containing oxetanes, cycloaliphatic epoxides, and polyols.The photopolymerization rate is significantly higher for these novelepoxy resins than a conventional epoxidized vegetable or seed oil.

In one embodiment, the invention relates to an epoxy resin which is thereaction product of a polyol having 4 or more hydroxyl groups; and anethylenically unsaturated fatty acid, optionally a saturated fatty acid,or mixtures thereof; where at least one ethylenically unsaturated groupof the ethylenically unsaturated fatty acid is oxidized to an epoxygroup. The polyol having 4 or more hydroxyl groups may be, for example,pentaerythritol, di-trimethylolpropane, di-pentaerythritol,tri-pentaerythritol, sucrose, glucose, mannose, fructose, galactose,raffinose, copolymers of styrene and allyl alcohol, polyglycidol andpoly(dimethylpropionic acid); and the ethylenically unsaturated fattyacid, optionally a saturated fatty acid, or mixtures thereof may be avegetable or seed oil. In one embodiment, the polyol is sucrose and thevegetable or seed oil is selected from coconut oil, corn oil, castoroil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oilfatty acid, tung oil, vernonia oil, and mixtures thereof. In oneembodiment, the polyol is sucrose and the oil is soybean oil. The degreeof esterification may be varied. The polyol may be fully esterified,where substantially all of the hydroxyl groups have been esterified withthe fatty acid, or it may be partially esterified, where only a fractionof the available hydroxyl groups have been esterified. Similarly, thedegree of epoxidation may be varied from substantially all to a fractionof the available double bonds.

The epoxy resins of the invention may be derivatized by ring-openingreactions of at least a portion of the epoxy groups to form resinshaving different functional groups. In one embodiment, the epoxy resinis reacted with an ethylenically unsaturated acid to introduceethylenically unsaturated groups. A resin having hydroxyl functionalityis another embodiment of the invention which is the reaction product ofan epoxy resin of the invention and at least one organic acid or atleast one alcohol. The degree of derivatization may also be varied. Insome embodiments substantially all of the epoxy groups may bederivatized while in others only a fraction of the available epoxygroups may be derivatized.

Methods of making of the epoxy resin, and each of its derivative resins,are separate embodiments of the invention. Coating compositions andcoated objects using each of the resins are further embodiments of theinvention. An epoxy-anhydride composition, a further embodiment of theinvention, comprises an epoxy resin of the invention, an acid anhydride,and a tertiary amine catalyst.

BRIEF DESCRIPTIONS OF THE FIGURES

FIG. 1 depicts an exemplary epoxidation of a sucrose fatty acid esteraccording to the invention.

FIG. 2 shows the effect of cis configuration of double bonds andepoxides on fatty acid morphology.

FIG. 3 depicts an exemplary epoxy-anhydride curing reaction.

FIG. 4 depicts a Photo-DSC thermogram of a coating formulationcontaining ESE/ESO (Set I) from Example 2.

FIG. 5 depicts a Photo-DSC thermogram of a coating formulationcontaining ESE/ESO and UVR 6110 (Set II) from Example 2.

DESCRIPTION OF THE INVENTION

Highly functional epoxy resins of the invention are prepared from theepoxidation of vegetable oil fatty acid esters of polyols having >4hydroxyl groups/molecule. Polyol esters of fatty acids, PEFA's,containing four or more vegetable oil fatty acid moieties per moleculecan be synthesized by the reaction of polyols with 4 or more hydroxylgroups per molecule with either a mixture of fatty acids or esters offatty acids with a low molecular weight alcohol, as is known in the art.The former method is direct esterification while the latter method istransesterification. A catalyst may be used in the synthesis of thesecompounds. As shown in FIG. 1 with sucrose, as an exemplary polyol to beused in the invention, esterified with a vegetable oil fatty acid,epoxide groups may then be introduced by oxidation of the vinyl groupsin the vegetable oil fatty acid to form epoxidized polyol esters offatty acids, EPEFA's. The epoxidation may be carried out using reactionsknown in the art for the oxidation of vinyl groups with in situepoxidation with peroxyacid being a preferred method.

Polyols having at least 4 hydroxyl groups per molecule suitable for theprocess include, but are not limited to, pentaerythritol,di-trimethylolpropane, di-pentaerythritol, tri-pentaerythritol, sucrose,glucose, mannose, fructose, galactose, raffinose, and the like.Polymeric polyols can also be used including, for example, copolymers ofstyrene and allyl alcohol, hyperbranched polyols such as polyglycidoland poly(dimethylpropionic acid), and the like. Exemplary polyols areshown below in Scheme 3 with the number of hydroxyl groups indicated by(f). Comparing sucrose to glycerol, there are a number of advantages forthe use of a polyol having more than 4 hydroxyl groups/moleculeincluding, but not limited to, a higher number of fatty acids/molecule;a higher number of unsaturations/molecule; when epoxidized, a highernumber of oxiranes/molecule; and when crosslinked in a coating, highercrosslink density.

The degree of esterification may be varied. The polyol may be fullyesterified, where substantially all of the hydroxyl groups have beenesterified with the fatty acid, or it may be partially esterified, whereonly a fraction of the available hydroxyl groups have been esterified.It is understood in the art that some residual hydroxyl groups mayremain even when full esterification is desired. In some applications,as discussed below, residual hydroxyl groups may provide benefits to theresin. Similarly, the degree of epoxidation may be varied fromsubstantially all to a fraction of the available double bonds. Thevariation in the degree of esterification and/or epoxidation permits oneof ordinary skill to select the amount of reactivity in the resin, bothfor the epoxidized resins and their derivatives.

The hydroxyl groups on the polyols can be either completely reacted oronly partially reacted with fatty acid moieties. Any ethylenicallyunsaturated fatty acid may be used to prepare a polyol ester of fattyacids to be used in the invention, with polyethylenically unsaturatedfatty acids, those with more than one double bond in the fatty acidchain, being preferred. The Omega 3, Omega 6, and Omega 9 fatty acids,where the double bonds are interrupted by methylene groups, and the seedand vegetable oils containing them may be used to prepare polyol esterof fatty acids to be used in the invention. Mixtures of fatty acids andof vegetable or seed oils, plant oils, may be used in the invention. Theplant oils, as indicated above, contain mixtures of fatty acids withethylenically unsaturated and saturated fatty acids possibly presentdepending on the type of oil. Examples of oils which may be used in theinvention, include but are not limited to, corn oil, castor oil, soybeanoil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid,tung oil, vernonia oil, and mixtures thereof. As discussed above, thepolyol fatty acid ester may be prepared by direct esterification of thepolyol or by transesterification as is known in the art. The doublebonds on the fatty acid moieties may be converted into epoxy groupsusing known oxidation chemistry yielding highly functional epoxy resins,EPEFA's—epoxidized polyol esters of fatty acids. Table 2 lists thedouble bond functionality of some representative fatty acid esters(=/FA) based upon the number of esterified hydroxyl groups (f).

TABLE 2 Double Bond Functionality of Fatty Acids in Selected OilsFunctionality of = for FA esters Avg. = having the indicated FAfunctionality Oil /FA f = 3 f = 4 f = 6 f = 8 Soybean 1.54 4.62 6.169.24 12.32 Safflower 1.66 4.98 6.64 9.96 13.28 Sunflower 1.39 4.17 5.568.34 11.12 Linseed 2.10 6.30 8.40 12.60 16.80 Tall Oil 1.37 4.11 5.488.22 10.96 Fatty Acid

The geometry of the double bonds in naturally occurring plant oil fattyacids are in the cis configuration, in which the adjacent hydrogen atomsare on the same side of the double bond. One interesting feature of thedouble bond in these ethylenically unsaturated fatty acid chains is thatit puts a “kink” in the chain (FIG. 2 a). For example, linolenic acidcan be significantly bent by three “kinks” of three cis double bonds.Peroxyacids transfer oxygen to the double bonds with synstereochemistry. The reaction is stereospecific, in which cis doublebonds yield cis epoxides. The main effect of epoxidation on the alkenecarbons is to transform their hybridization from sp² to sp³ (FIG. 2 b).

The polyol esters used in the invention, and particularly sucroseesters, have compact macromolecular structures, due to the compactstructure of the polyol core and the generally uniform distribution offatty acids around the core. Since the presence of cis double bonds andepoxides can vary the extension of the fatty acid chains, the amount ofdouble bonds and epoxides surely influences the overall dimension ofsucrose ester macromolecules. Therefore, the morphology of sucroseesters is influenced by the morphology of its up to eight fatty acidchains.

A dilute solution of polyol ester molecules, such as sucrose estermolecules, can be thought of as their equivalent spheres. They areuniform, rigid, and non-interacting. For example, the intrinsicviscosity of sucrose esters reflects the hydrodynamic volume of theirequivalent spheres. For fully substituted sucrose esters, it was foundthat 1) epoxidized sucrose esters have higher intrinsic viscosities thantheir corresponding sucrose esters, and 2) higher amounts of epoxideresult in higher intrinsic viscosities. These observations indicate thatthe hydrodynamic volume of the sucrose ester molecules is increased byepoxidation and that the higher epoxide content results in largerdimension molecules.

In addition to the larger volume for the epoxidized polyol esters,intermolecular forces, such as van der Waals forces and dipole-dipoleinteractions, can be invoked for understanding the observations of bulkviscosity and density of the sucrose esters. Not only does epoxidationincrease the molecular weight of polyol esters, the polarity of thepolyol esters also increases. Thus, the epoxidized polyol estermolecules, especially epoxidized sucrose ester molecules, can interactmore extensively, leading to a higher bulk viscosity and higher density.Since even in the “fully substituted” sucrose esters there are someresidual hydroxyl groups, hydrogen bonding may also occur between themolecules. Indeed, the bulk viscosity and density of the partiallysubstituted epoxidized sucrose ester is higher than its fullysubstituted counterpart, due to the additional hydrogen bonding. Thisincrease in polarity is also reflected in a more well-defined glassystate as is indicated by the sharp glass transitions observed.

The epoxidation of sucrose esters of ethylenically unsaturated vegetableoil fatty acids has resulted in unique biobased resins having a highconcentration of epoxy groups. As has been seen, functionalities of 8 to15 epoxide groups per molecule may be achieved, depending on thecomposition of the fatty acid used and the degree of substitution of thefatty acids on the sucrose moiety. This is substantially higher thanwhat can be achieved through epoxidation of triglycerides which rangefrom about 4 for epoxidized soybean oil up to 6 for epoxidized linseedoil.

The high epoxide functionality of these resins coupled with the rigidityof a polyol having at least 4 hydroxyl groups per molecule, such assucrose, has significant implications for the use of these resins andtheir derivatives in applications such as thermosetting materials. Withthe epoxidized polyol esters of fatty acids, EPEFA's, crosslinkedmaterials having an outstanding combination of properties can beachieved.

Another embodiment of the invention relates to a resin which is aderivative of an EPEFA from the ring-opening reaction of the EPEFA withan ethylenically unsaturated acid, acrylated EPEFA's, and the use ofsuch acrylated derivatives in coating compositions. The acrylation of anEPEFA may be done by a ring-opening reaction of the epoxy rings of theEPEFA with an ethylenically unsaturated acid monomer by methods knownthe art. Acid-epoxy catalyst is used to increase the rate of reaction.See Bajpai, et al., Pigment & Resin Technology 2004, 33, 160.Ethylenically unsaturated acid monomers such as acrylic acid,methacrylic acid, crotonic acid, and the like, and mixtures thereof, maybe used. The acrylate groups in the acrylated EPEFA molecules (AEPFA's)functionalize the molecules to participate in free-radicalpolymerization in a coating composition. Ethylenically unsaturateddiacids such as maleic acid, fumaric acid, and itaconic acid may also beused, alone, in mixtures, and in combination with ethylenicallyunsaturated acid monomers such as those just discussed, to introduceunsaturation and additional acid functionality.

The extent of reaction of the epoxy groups in the EPEFA withethylenically unsaturated acids may be varied by varying the amount ofethylenically unsaturated acid used in the reaction. For example aslittle as 10% or less of the epoxy groups may be reacted up to as muchas 100% of the epoxy groups, resulting in resins having varying degreesof ethylenically unsaturated functionality. As is known in the art,numerous catalysts can be used to catalyze the acid-epoxy reaction andare reviewed in Blank, et al., J. Coat. Tech., 2002, 74, 33-41. Basesknown to catalyze acid-epoxy reactions, such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), triethyl amine, pyridine,potassium hydroxide and the like may be used. Quaternary ammonium andquaternary phosphonium compounds can also be used to catalyze thereaction. In addition salts and chelates of metals such as aluminum,chromium, zirconium, or zinc may also be used. Catalysts AMC-2 and ATC-3available from AMPAC Fine Chemicals are chelates of chromium andeffective catalyst for acid-epoxy reactions.

In a further embodiment of the invention, an EPEFA may undergo aring-opening reaction with an organic acid in acid-epoxy reaction, as isknown in the art, to introduce hydroxyl functionality and form thecorresponding EPEFA polyol. Introducing hydroxyl functionality at anepoxy group using base-catalyzed acid-epoxy reactions is known in theart. Organic acids which may be used include, for example, acetic acid,propionic acid, butyric acid, isobutyric acid, 2-ethylhexanoic acid, andmixtures thereof. Small, C₁-C₁₂, organic acids such as these aregenerally preferred but others may also be used. As discussed above, anumber of catalysts can be used to catalyze an acid-epoxy reaction andare reviewed in Blank, et al., J. Coat. Tech., 2002, 74, 33-41. Basesknown to catalyze acid-epoxy reactions, such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), triethyl amine, pyridine,potassium hydroxide and the like may be used. Quaternary ammonium andquaternary phosphonium compounds can also be used to catalyze thereaction. In addition salts and chelates of metals such as aluminum,chromium, zirconium, or zinc may also be used. Catalysts AMC-2 and ATC-3available from AMPAC Fine Chemicals are chelates of chromium andeffective catalyst for acid-epoxy reactions.

The extent of reaction of the epoxy groups in the EPEFA with organicacids may be varied by varying the amount of organic acid used in thereaction. For example, as little as 10% or less of the epoxy groups maybe reacted up to as much as 100% of the epoxy groups, resulting inpolyols having varying degrees of hydroxyl functionality.

In a further embodiment of the invention, an EPEFA may undergo aring-opening reaction with an organic alcohol to introduce hydroxylfunctionality and form the corresponding EPEFA polyol. Organic alcoholswhich may be used include methanol, ethanol, n-propanol, n-butanol,isopropanol, isobutanol, 2-ethyl-1-hexanol, and the like as well asmixtures thereof. The resulting EPEFA polyol may be reacted with apolyisocyanate to form a thermoset polyurethane coating in the same wayas conventional polyols known in the art.

The extent of reaction of the epoxy groups in the EPEFA with alcohol maybe varied by varying the amount of alcohol used in the reaction. Forexample, as little as 10% or less of the epoxy groups may be reacted upto as much as 100% of the epoxy groups, resulting in polyols havingvarying degrees of hydroxyl functionality.

The resulting EPEFA polyol may be reacted with a polyisocyanate to forma thermoset polyurethane coating in the same way as conventional polyolsknown in the art. Any compound having two or more isocyanate groups canbe used as a crosslinker. Aromatic, aliphatic, or cycloaliphaticisocyanates are suitable. Examples of isocyanates which can be used forcrosslinking the polyols are hexamethylene diisocyanate, isophoronediisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate,meta-tetramethylxylylene diisocyanate and the like. Adducts or oligomersof the diisocyanates are also suitable such as polymeric methylenediphenyl diisocyanate or the biuret or isocyanurate trimer resins ofhexamethylene diisocyanate or isophorone diisocyanate. Adductpolyisocyanate resins can be synthesized by reacting a polyol with adiisocyanate such that unreacted isocyanate groups remain. For example,one mole of trimethyolopropane can be reacted with three moles ofisophorone diisocyanate to yield an isocyanate functional resin.

Catalysts known in the art may be used to increase the curing speed of apolyol with a polyisocyanate to form polyurethane. Salts of metals suchas tin, bismuth, zinc and zirconium may be used. For example, dibutyltin dilaurate is a highly effective catalyst for polyurethane formation.Tertiary amines may also be used as a catalyst for urethane formation asis known in the art, such as for example, triethyl amine, DABCO[1,4-diazabicyclo[2.2.2]octane], and the like.

Another embodiment of the invention relates to epoxy-anhydride curingcompositions comprising an EPEFA (discussed above), an acid anhydride,and a curing catalyst, such as a tertiary amine catalyst known in theart. In this embodiment, the EPEFA's of the invention used as theepoxy-functional molecule in an epoxy-anhydride curing composition.

Any acid anhydride, such as those used in coatings applications, may beused to prepare an epoxy-anhydride coating composition of the invention.Examples of acid anhydrides which may be used include, but are notlimited to, succinic anhydride, maleic anhydride,4-Methyl-1,2-cyclohexanedicarboxylic anhydride (MCHDA), dodecynylsuccinic anhydride, phthalic anhydride (PA), tetrahydrophthalicanhydride (THPA), hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (Me-THPA), methyl hexahydrophthalicanhydride (Me-HHPA), trialkyl tetrahydrophthalic anhydride (TATHPA),trimellitic anhydride, chlorendic anhydride, nadic methyl anhydride(methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride),pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride andmixtures thereof. Preferred are those anhydrides which are liquid andmiscible with the EPEFA resins.

Tertiary amine catalysts known in the art may be used in the coatingcompositions of the invention. Tertiary amine catalysts include at leastone tertiary nitrogen atom in a ring system. Examples of tertiary aminecatalysts include but are not limited to as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane(DABCO), 4-(dimethylamino)pyridine (DMAP),7-methyl-1.5.7-triazabicyclo[4.4.0]dec-5-ene (MTBD), quinuclidine,pyrrocoline and similar materials.

The ratio of epoxy equivalents in the EPEFA to anhydride equivalents canbe varied in order to vary the crosslink density and the properties ofthe thermoset.

In the examples below, epoxidized sucrose esters fatty acids, ESEFAs,derived from different vegetable oils (i.e. linseed, safflower, andsoybean) and different substitution of sucrose esters of fatty acids,SEFAs, (i.e. sucrose soyate B6) were used to formulate epoxy-anhydridecuring systems. 4-Methyl-1,2-cyclohexanedicarboxylic anhydride (MCHDA)was used as the anhydride, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)was used as a specified tertiary amine catalyst. A commercial product,Vikoflex 7170 epoxidized soybean oil (ESO), was used as the control todemonstrate the innovative concept of using ESEFAs in this study. Bycomparing with the control, the epoxy-anhydride curing based on theutilization of ESEFAs as the epoxy compounds proved to be veryimpressive.

FIG. 3 shows the main reactions that take place on curing ESEFA-MCHDA inthe presence of amidine catalyst and trace hydroxyls. There are tworeactions to initiate the polyester network formation: (a) DBU reactswith anhydride to create carboxylate; (b) hydroxyl reacts with anhydrideto create carboxylic acid. In FIG. 3, R represents the organic moietieson the tertiary amine catalyst, R₃N, such as those on the tertiaryamines described above. R₁ and R₂ represent the organic moieties on theacid anhydride, such as those discussed above.

A further embodiment of the invention involves the cationicpolymerization of the epoxy groups in the EPEFA resins. Coatingformulations can be prepared by mixing the epoxy resins with aphotoinitiator, and optionally, a diluent resin.

It has been found that cationic photopolymerization of the epoxidizedhigh functional resins yields films having greater hardness than thosemade from epoxidizied vegetable oils. In addition, surprisingly, thecrosslinking reaction occurs at a faster rate for the highly functionalepoxy resins than epoxidized vegetable oils.

Diluent resins can be low molecular weight epoxy resins such as thediglycidyl ether resins of bisphenol-A, cycloaliphatic epoxy resins,monofunctional epoxy resins, and the like. Oxetane-based compounds suchas 3-hydroxymethyl, 3-ethyl oxetane,bis{[1-ethyl(3-oxetanyl)]methyl}ether, and the like, can also be used asdiluent resins.

Hydroxy functional compounds can also serve as diluent resins. These caninclude alcohols such as butanol, 2-ethyl hexanol,1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and the like.Polymeric polyols can also be used as diluents. These can be polyetherpolyols such as polyethylene glycols, polypropylene glycols,polytetramethylene diols. Polyester polyols such as polycaprolactonescan also be incorporated as diluents.

Examples of photoinitiators used for effecting the cationicphotopolymerization of the coating mixture are the diaryliodonium salts,triarylsulfonium salts, diaryliodosonium salts, dialkyl phenylsulfoniumsalts, dialkyl(hydroxydialkylphenyl)-sulfonium salts and ferroceniumsalts.

A further embodiment of the invention involves the free radical curingof the acrylated EPEFA resins. Formulations may be prepared by mixingthe acrylated EPESA resin with an optional diluent, an optional solvent,and a photoinitiator.

When a coating composition contains an acrylated EPEFA, diluents thediluents may be ones used in free radical or vinyl polymerizations suchas but not limited to, isodecyl acrylate, 2-hydroxyethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, 1,6-hexanediol diacrylate,trimethylolpropane triacrylate, pentaerythritol tetraacrylate,ethoxylated trimethylolpropane triacrylate, and acrylated epoxidizedsoybean oil.

For curing of the acrylated EPEFA compounds and formulations, a freeradical photoinitiator is needed. Suitable free radical photoinitiatorsinclude cleavage or Norrish I type photoinitiators or Norrish type IIphotoinitiators known in the art. Examples of Norrish type Iphotoinitiators are 2-hydroxy-2-methyl-1-phenyl-1-propanone,2,2-diethoxyacetophenone, benzildimethylketal,1-hydroxycyclohexylphenyl-ketone, 2,2′dimethoxy-2-phenylacetophenone andthe like, Examples of Norrish type II photoinitiators are benzophenone,benzio, xanthone, thioxanthone, and the like, combined with synergistssuch as triethanolamine, triethylamine, dimethylethanol amine, and thelike.

The invention also relates to the use of a coating composition which maybe coated onto a substrate and cured using techniques known in the art.The substrate can be any common substrate such as paper, polyester filmssuch as polyethylene and polypropylene, metals such as aluminum andsteel, glass, urethane elastomers, primed (painted) substrates, and thelike. The coating composition of the invention may be cured thermally orphotochemically, e.g. UV or electron beam cure.

Pigments and other additives known in the art to control coatingrheology and surface properties can also be incorporated. For example acoating composition of the invention may further contain coatingadditives. Such coating additives include, but are not limited to, oneor more leveling, rheology, and flow control agents such as silicones,fluorocarbons or cellulosics; extenders; reactive coalescing aids suchas those described in U.S. Pat. No. 5,349,026, incorporated herein byreference; plasticizers; flatting agents; pigment wetting and dispersingagents and surfactants; ultraviolet (UV) absorbers; UV lightstabilizers; tinting pigments; colorants; defoaming and antifoamingagents; anti-settling, anti-sag and bodying agents; anti-skinningagents; anti-flooding and anti-floating agents; biocides, fungicides andmildewcides; corrosion inhibitors; thickening agents; or coalescingagents. Specific examples of such additives can be found in RawMaterials Index, published by the National Paint & Coatings Association,1500 Rhode Island Avenue, N.W., Washington, D.C. 20005. Further examplesof such additives may be found in U.S. Pat. No. 5,371,148, incorporatedherein by reference.

Solvents may also be added to the coating formulation in order to reducethe viscosity. Hydrocarbon, ester, ketone, ether, ether-ester, alcohol,or ether-alcohol type solvents may be used individually or in mixtures.Examples of solvents can include, but are not limited to benzene,toluene, xylene, aromatic 100, aromatic 150, acetone, methylethylketone, methyl amyl ketone, butyl acetate, t-butyl acetate,tetrahydrofuran, diethyl ether, ethylethoxy propionate, isopropanol,butanol, butoxyethanol, and so on.

EXAMPLES

Methods:

The following methods are used in the examples for the characterizationof the compounds synthesized and materials prepared.

Molecular weight was determined by gel permeation chromatography (GPC)using a Waters 2410 system equipped with refractive index detector.Polystyrene standards were used for calibration. A 1.5% sample solutionin THF using a flow rate of 1 ml/min was used.

MALDI-TOF (matrix assisted laser desorption ionization-time of flight)mass spectra were recorded on a Bruker Ultraflex II spectrometerequipped with a 1.85 m linear flight tube and a Smart beam laser. Allmass spectra were obtained in positive ion and linear mode. Samples weredissolved in THF (1 mg/mL), and α-cyano-4-hydroxycinnamic acid (10 mg/mLin THF) was used as matrix, and trifluoroacetic acid (0.1 wt % in water)was used as the dopant. A mixture of 10 μL of the matrix solution, 2 μLof the dopant, and 2 μL of the polymer solution was prepared and a 2 μLsample was spotted on the target plate. All data were processed usingFlex analysis and PolyTools software package.

FTIR measurements were done by a Thermo Nicolet 8700 FTIR spectrometer.Spectra acquisitions were based on 32 scans with data spacing of 4.0cm⁻¹ in the range of 4000-500 cm⁻¹.

NMR measurements were done at 23° C. using a JOEL-ECA (400 MHz) NMRspectrometer with an auto sampler accessory. All measurements were madeusing CDCl₃ as solvent. The data was processed using the Delta softwarepackage.

The bulk viscosities of samples were measured using a BrookfieldViscometer (DV-II+Pro) at 21° C.

Intrinsic viscosity [η] of the materials was measured in THF with aCannon-Fenske viscometer (size 50) at 25° C. The concentration ofsolution was 3.7-9.0 g/100 mL, and the relative viscosity η_(r) wascontrolled in the good range of 1.1-1.6. The extrapolations of reducedviscosity and inherent viscosity were averaged to yield the intrinsicviscosity for each sample.

The densities of samples were measured using a BYK-Gardner Weight PerGallon Cup at 25° C., referring to ASTM D 1475. The Midget Cup having acapacity of 8.32 grams of water at 25° C. was used. The net weight ofthe fluid sample in grams equals the sample's density in pounds per U.S.gallon, which is converted into grams/mL.

A DSC 01000 from TA Instruments (New Castle, Del.) with an auto samplerwas used for glass transition temperature (T_(g)) determination. Sampleswere subjected to a heat-cool-heat cycle from −90 to +100° C. by rampingat 10° C./min for both heating and cooling cycles. The second heatingcycle was used to characterize the samples.

Iodine values were determined according to ASTM D 5768.

Epoxide equivalent weight (EEW, g/eq.) of the epoxy products wasdetermined by epoxy titration according to ASTM D 1652.

Acid value is measured according to ASTM D 465.

Photo-DSC experiments were obtained using a 01000 Differential Scanningcalorimeter (TA Instruments) equipped with a photo-calorimeteryaccessory (PCA). The experiment was run under 25° C. and with 1 minexposure time. The intensity of the UV light source was 50 mW/cm². ThePhoto-DSC was followed by a regular DSC scan with temperature range of−50° C. to 200° C. at a ramp of 10° C./min. A heating, cooling andheating cycle were monitored.

Impact test were measured according to ASTM D 2794 using a BYK-GardnerHeavy Duty Impact Tester Model IG-1120, with a 1.8 kg (4 lb) mass and1.27 cm (0.5 in) diameter round-nose punch.

A BYK-Gardner pendulum hardness tester was used to measure the Konigpendulum hardness of the cured film in accordance with ASTM D 4366.

MEK double rubs of the cured film was done in accordance with ASTM D5402.

The film thickness was measured with a Byko-test 8500.

König pendulum hardness and pencil hardness were measured using ASTM D4366-95 and ASTM D 3363-00, respectively.

The adhesion of coatings on steel substrate was evaluated usingcrosshatch adhesion ASTM D 3359-97.

Mandrel bend test was carried out based on ASTM D 522, and the resultswere reported as the elongation range of coating at cracking.

For tensile testing, die-cut specimens were prepared from the thin films(0.10-0.16 mm) and thick samples (1.6-2.0 mm) according to ASTM D 638.The tensile tests were carried out at 25° C. using Instron 5542(Norwood, Mass.). The grip separation distance of the tensile testingwas 25.4 mm, and the effective gauge length was 20.4 mm. The crossheadspeed was 0.1% elongation/sec. (0.0204 mm/sec.). The tensile propertiesof each sample were reported as the average of 5 measurements taken atdifferent specimens and the uncertainty was the standard deviation.

Dynamic mechanical properties of thermosetting films were measured intension mode using 0800 DMA from TA Instruments (New Castle, Del.).Rectangular specimens with dimensions of 20 mm length, 5 mm width, and0.10-0.16 mm thickness were prepared. The measurements were performedfrom −110 to 200° C. at a heating rate of 5° C./min and frequency of 1Hz. The glass transition temperature (T_(g)) was determined as thetemperature at the maximum of tan δ vs. temperature curve. The storagemodulus (E′) in the rubbery plateau region was determined at generally60° C. above the glass transition temperature. The crosslink density(v_(e)) of thermoset was calculated using E′ in the rubbery plateauregion by the following equation, derived from the theory of rubberelasticity: where E′ is the storage modulus of the thermoset in therubbery plateau region at T_(g)+60° C., R is the gas constant, and T isthe absolute temperature.

E′=3

_(e) RT

Example 1 Preparation of Epoxidized Sucrose Esters (ESE) of Fatty Acids

1.1 Starting Materials:

The sucrose esters of fatty acids (SEFA's) were received from Procter &Gamble Chemicals (Cincinnati, Ohio). Acetic acid (ACS reagent, 99.7%),diethyl ether (ACS reagent, ≧99.0%), hydrogen peroxide (50 wt % solutionin water), Amberlite IR-120H ion-exchange resin, sodium carbonate (ACSreagent), and anhydrous magnesium sulfate (reagent grade, ≧97%) werepurchased from Sigma-Aldrich, Inc. (St. Louis, Mo.). All materials wereused as received without further purification.

1.2 Method:

Four SEFOSE sucrose esters derived from different vegetable oils(Table 1) were epoxidized using peracetic acid generated in situ fromhydrogen peroxide and acetic acid, in the presence of Amberlite IR 120Has catalyst using the method described below for the epoxidation ofsucrose linseedate. Table 3 lists the sucrose esters of fatty acids. Theepoxidation reactions were carried out in a 500 mL four-neck flask,equipped with a mechanical stirrer, a nitrogen inlet, a thermocouple andan addition funnel.

TABLE 3 Sucrose Esters of Fatty Acids Used. Average Name The type ofdegree of Iodine Viscosity Full Abbreviated plant oil substitutionvalue, IV₀ (mPa · s) Sucrose linseedate SL Linseed 7.7 177 236 SucroseSSF Safflower 7.7 133 393 safflowerate Sucrose soyate SS Soybean 7.7 117425 Sucrose soyate B6 SSB6 Soybean 6.0 115 890

Sucrose linseedate (170 g, 0.07 mol) containing 1.17 mol double bonds,acetic acid (35.1 g, 0.585 mol), and Amberite 120H (34 g, 20 wt % ofsucrose linseedate) were charged to the reaction flask. The molar ratioof acetic acid:hydrogen peroxide (H₂O₂):double bond was controlled as0.5:2:1. The mixture was rapidly stirred and nitrogen purged, and thetemperature was raised to 55° C. Hydrogen peroxide (50 wt % aqueoussolution, 160 g, 2.35 mol) was added dropwise using an addition funnelat a rate such that the reaction temperature was controlled in the rangeof 55-65° C. After the completion of the hydrogen peroxide addition, thereaction was stirred at 60° C. for 30 minutes. The product wastransferred into a separatory funnel and allowed to cool to roomtemperature. After the aqueous layer was drained, the organic layer wasdiluted by 300 mL diethylene ether and washed with water five times. Asaturated sodium carbonate/water solution was used as the last wash tocompletely remove the acetic acid. The organic layer was transferredinto a beaker and dried with anhydrous magnesium sulfate overnight. Thehydrated magnesium sulfate was removed by filtration, and diethyleneether was removed by rotavapping. Finally, a transparent viscous liquidwas obtained as the epoxidized sucrose linseedate. The other SEFAs(sucrose safflowerate, sucrose soyate, and sucrose soyate B6) wereepoxidized and purified using the same process. The recovered yieldswere all about 97 percent.

1.3 Results:

The SEFOSE sucrose esters used in this example are initially amberliquids, and sucrose linseedate and sucrose soyate B6 are darkerbrownish-yellow. The abbreviated name of the epoxidized sucrose ester isdefined by adding an E in front of the abbreviated name of thecorresponding sucrose ester. The four epoxidized sucrose esterssynthesized by the above method are: epoxidized sucrose linseedate(ESL), epoxidized sucrose safflowerate (ESSF), epoxidized sucrose soyate(ESS), and epoxidized sucrose soyate B6 (ESSB6). Due to theepoxidization of double bonds and the bleaching action of the peroxide,the epoxidized sucrose esters are all colorless. It is commonly observedthat epoxidized vegetable oils tend to become hazy on standing due tocrystallization during storage. However, the epoxidized sucrose estersremain transparent during storage with no haze formation observed afterseveral months.

Characterization of the products using proton and carbon 13 NMR and FTIRall indicated that the expected products had been successfullysynthesized.

The conversion of double bonds, epoxide equivalent weights, and epoxidefunctionalities for the ESE resins synthesized are shown in Table 4. Theiodine value (IV) can be used to determine the conversion of doublebonds to epoxides using equation (1), where IV₀ is the iodine value ofthe starting sucrose ester, and IV_(f) is the iodine value of the epoxyproduct. The conversion of double bonds to epoxy groups for all resinswas greater than 99 percent.

$\begin{matrix}{{\% \mspace{14mu} {Conversion}} = {100 \times \frac{{IV}_{0} - {IV}_{f}}{{IV}_{0}}}} & (1)\end{matrix}$

The epoxide functionality (EF) of the epoxy products can be estimatedusing the epoxide equivalent weight (EEW) and MALDI-TOF molecular weightvalues using equation (2), where W_(i) is the average MW of epoxidizedsucrose ester with the degree of substitution i. For fully substitutedepoxidized sucrose esters, i equals 8. For epoxidized sucrose soyate B6,i equals 6.

$\begin{matrix}{{EF} = \frac{W_{i}}{EEW}} & (2)\end{matrix}$

The epoxide functionality is higher for those sucrose ester resinshaving higher amounts of double bonds, as would be expected. It islowest for the partially substituted sucrose soyate resin, SSB6, sinceonly six of the eight available hydroxyls on sucrose are substitutedwith the ethylenically unsaturated soya fatty acid. The epoxidefunctionality is quite high for these resins; much higher than can beachieved through epoxidization of triglyceride oils such as soybean oil,where the epoxy functionality would be around 4.4.

TABLE 4 Properties of the epoxidized sucrose esters of fatty acids(ESEFAs). Epoxy W_(i) EEW Epoxide product IV_(f) % Conversion (g/mol)(g/eq.) functionality ESL 0.16 99.9 2,701 180 15.0 ESSF 0.32 99.8 2,651228 11.6 ESS 0.44 99.6 2,623 248 10.6 ESSB6 0.73 99.4 2,048 256 8.0

Example 2 UV-Curable Coating Formulations of Epoxidized Sucrose Estersof Fatty Acids

2.1 Materials and Methods:

The epoxidized sucrose linseedate (ESL), epoxidized sucrose safflowerate(ESSf) and epoxidized sucrose soyate (ESSy) were synthesized followingthe method in Example 1. UVR 6110,3,4-epoxycyclohexylmethyl-3,4-epoxyhexane carboxylate, UVI 6974, amixture of triarylsulfonium hexafluoroantimonate salts were obtainedfrom Dow Chemical Company, USA. Oxt-101, 3-ethyl-3-hydroxymethyl oxetane(TMPO) was supplied by Togoasei America Inc. Epoxidized soybean oil(ESO) was procured from Arkema, USA. The properties of ESL, ESSy, ESSyand ESO are shown in Table 5.

TABLE 5 Viscosity and Epoxy Equivalent Weight of ESEs and ESO EpoxyEquivalent Epoxy Viscosity Sample Weight (g/mole) groups/mole (mPa · s)ESL 183.31 14.18 8000 ESSf 229.56 11.33 5100 ESSy 252.19 10.31 2190 ESO243.52 4.4 972

2.2 Coating Formulation:

The coating formulations are listed in Table 6. All formulationscontained a cationic photoinitiator (UVI 6974) and a reactive diluent,Oxt-101. Formulations A-D contain the ESEs and ESO as the primary resinswhile formulations E-H contain a mixture of ESE/ESO and cycloaliphaticdiepoxide UVR 6110. The coating formulations were mixed thoroughly in ahomogenizer. The compatibility of the coating solutions are also shownin Table 4. UV-cured coating samples were obtained by passing 3 mil wetfilms on bare steel panels once (10 s) through a UV beam using a FusionCure System. The intensity was measured by UV Power Puck II as 1400mW/cm².

TABLE 6 Coating Formulations Components Set I Set II (wt %) A B C D E FG H ESL — 57.9 — — — 51.5 — — ESSf 57.9 — — — 51.5 — — — ESSy — — 57.9 —— — 51.5 — ESO — — — 57.9 — — — 51.5 UVR 6110 — — — — 6.4 6.4 6.4 6.4Oxt-101 38.6 38.6 38.6 38.6 38.6 38.6 38.6 38.6 UVI 6974 3.5 3.5 3.5 3.53.5 3.5 3.5 3.5 Solubility Clear Clear Clear Clear Clear Clear ClearHazy

2.3 Results and Discussion:

Photo-DSC is an effective tool for the kinetic analysis ofphotopolymerization (Chen, et al., Polymer 2002, 43, 5379; Zong, et al.,J. Polym. Sci., Part A: Polym. Chem., 41 (2003), 3440; Cho, et al.,Polym. Test. 2002, 21, 781; Cho J.; Kim E.; Kim H.; Hong J. Polym. Test.2003, 22,633). The photo-DSC plot of the two set of formulations areshown in FIGS. 4 and 5. The exothermal peaks of the UV cured coatings inboth FIGS. 4 and 5 show that formulations C and G, both containing ESSy,have a shorter induction time and shortest time for peak maximumindicating the fastest reacting system (Hong J. W.; Lee H. W., J. KoreanInd. & Eng. Chem. 1994, 5, 857). The ESL and ESSf have almost equalcuring rate while ESO has the longest induction time and peak maximum.The higher curing rate of the ESSy can be attributed to the lessersteric strain of the epoxy groups to crosslink by ring opening reaction(Sangermano M.; Malucek G.; Priola A.; Manea M.; Prog. Org. Coat. 2006,55, 225). A very fast initial curing process leads to surface shrinkageand also since vitrification starts early, further diffusion of monomersis prevented (Sangermano M.; Malucek G.; Priola A.; Manea M.; Prog. Org.Coat. 2006, 55, 225). This results in a post curing effect which can beshown by further thermal treatment.

The properties of the cured coatings are given in Table 7. All of thecoatings based on epoxidized sucrose ester resins have higher T_(g),hardness, and solvent resistance than the control based on ESO. TheT_(g) of the ESL system is expectedly the highest showing maximumnetwork formation due to the high functionality of epoxy groups in theESL resin. In strong contrast, the T_(g) of the ESO system is below roomtemperature due to a lower amount of crosslinking due to lower epoxygroups per molecule. The ESL system also demonstrated the highesthardness and MEK double rubs showing an extensive crosslinked network.The ESO has low hardness and MEK double rubs showing that the coatinghas a lower crosslink density. In addition to the higher T_(g) and goodhardness, the coatings based on epoxidized sucrose esters also have goodimpact resistance. A consistent increase of the T_(g), hardness, andsolvent resistance of each system with the incorporation of UVR 6110 isalso observed.

TABLE 7 Coating Properties Reverse Glass Film König Impact MEKTransition thickness Hardness Resistance double Formulation Temp. (° C.)(μm) (s) (in-lb) rubs A 21.31 30.1 62 100 75 B 27.03 30.5 105 160 225 C15.69 30.3 48 80 58 D −0.63 30.5 35 172 45 E 23.15 30.4 77 80 86 F 44.7829.9 122 89 240 G 19.49 30.2 60 100 63 H 3.25 30.2 40 172 50

Example 3 Acrylation of an Epoxidized Sucrose Ester of a Fatty Acid

3.1 Materials:

Epoxidized sucrose soyate (ESSy) was prepared as in Example 1. AmpacFine Chemicals provided AMC-2 Accelerator. Isodecyl acrylated (IDA) and1,6-hexanediol diacrylate (HDODA) were obtained from Sartomer, while2-hydroxyethyl acrylate (HEA) was purchased from Sigma-Aldrich. Darocur®1173 photoinitiator was purchased from Ciba. Ebecryl 860, an acrylatedepoxidized soybean oil, was obtained from Cytec.

3.2 Synthesis

The epoxy equivalent weight of the Epoxidized Sucrose Soyate (ESSy) wasdetermined to be 248.79 g/mol. Acrylated resins were prepared havingthree different extents of acrylation (based on the number of epoxygroups). Table 8 contains the amount or reagents used for the acrylationof ESSy. AESSy is the fully acrylated resin, while PAESSy 50 indicatesthat 50 percent of the epoxy groups were acrylated and PAESSy indicatesthat 75 percent of the epoxy groups were acrylated.

TABLE 8 Acrylation of sucrose ester (SE) materials Hydroquinone (2.5% byweight Oxirane Extent of of oil + acrylic ESSy Content AcrylationAcrylic Acid acid) AMC-2 (1%) PAESSy 50 50.0 g 0.201 mol 50% 8.69 g 1.46g 0.581 g 0.121 mol PAESSy 75 50.0 g 0.201 mol 75% 10.9 g 1.52 g 0.609 g0.150 mol AESSy 50.0 g 0.201 mol 90% 13.0 g 1.58 g 0.630 g 0.181 mol

The required amount of ESSy, acrylic acid, 2.5% hydroquinone, and 1%AMC-2 were added in a three-necked 250 mL flask fitted with a condenser,thermometer, and a mechanical stirrer. Hydroquinone was added to preventthe homopolymerization of acrylate groups.⁹ AMC-2 catalyst was used inthe reaction. This catalyst is a mixture of 40-60% of phthalates esterand 40-60% of chromium 2-ethylhexanoate. The reaction mixture was heatedto a temperature of 90° C. The extent of acrylation was monitored bymeasuring the acid value. The reaction was stopped when the acid valuewas in the range of 5-15.

3.3 Coating Formulations Containing Acrylated Epoxidized Resin

Coating formulations consisting of Acrylated Epoxidized Resin (eitherEbecryl 860, PAESSy 50, PAESSy 75, or ASSy), solvents or diluents (20%by weight) to reduce viscosity, and Darocure 1173 (5% by weight) as thephotoinitiator were prepared and hand-mixed. They were applied ontoQ-panels (steel smooth finish, 0.020″×3″×6″) and glass panels (at athickness of about 40 μm using a film applicator. The coated panels werecured by exposing them to a UV lamp (Fusion LC6B Benchtop Conveyer withan F300 UV Lamp, intensity ˜1180 mW/cm² by UV Power Puck® II from EITInc) for 20 sec.

The properties of the coatings are listed in Tables 9-12. Coatings basedon acrylated epoxidized sucrose soyate (PAESSy 50, PAESSy 75, AESSy)have a high acrylate group functionality leading to coatings which arechemically resistive, hard, and inflexible. The hardness of the coatingsfrom the acrylated epoxidized sucrose ester resins is greater than thatof the acrylated epoxidized soybean oil based coatings. Overall, neitherthe degree of acrylation nor the type of diluents affected the coatingproperties significantly. The addition of diluents reduced viscosity by90%, yet no changes in coating properties were observed.

TABLE 9 AESO (Ebercryl 860) Coating Properties MEK IDA HEA HDODAHEA&HDODA Film thickness (μm) 51.3 42.8 47.5 37.5 39.6 König Hardness(s) 63 32 53 92 83 Reverse Impact 40 20 28 28 48 (inch-lb) PencilHardness HB F HB F HB MEK double rub >400 310 >400 >400 >400 Cross Hatch0B 0B 0B 0B 0B Adhesion Mandrel Bend >28% >28% >28% <3% ≈44%

TABLE 10 PAESSy 50 Coating Properties MEK IDA HEA HDODA HEA&HDODA Filmthickness (μm) 42.5 47.5 42.1 39.8 36.3 König Hardness (s) 67 30 40 8279 Reverse Impact 14 20 20 12 16 (inch-lb) Pencil Hardness B 2B 2B HB HBMEK double rub >400 298 >400 >400 >400 Cross Hatch 0B 0B 0B 0B 0BAdhesion Mandrel Bend ≈20% ≈25% ≈20% ≈4% ≈14%

TABLE 11 PAESSy 75 Coating Properties MEK IDA HEA HDODA HEA&HDODA Filmthickness (μm) 40.9 35.6 37.3 37.8 53.5 König Hardness (s) 100 75 108109 103 Reverse Impact 4 8 4 84 4 (inch-lb) Pencil Hardness B 2B B B BMEK double rub >400 117 >400 >400 >400 Cross Hatch 0B 0B 0B 0B 0BAdhesion Mandrel Bend <3% ≈14% ≈4% <3% <3%

TABLE 12 AESSy Coating Properties MEK IDA HEA HDODA HEA&HDODA Filmthickness (μm) 42.3 40.8 36.4 56.8 37.6 König Hardness (s) 88 85 106 88107 Reverse Impact 4 4 4 4 4 (inch-lb) Pencil Hardness B HB F F F MEKdouble rub >400 207 >400 >400 >400 Cross Hatch 0B 0B 0B 0B 0B AdhesionMandrel Bend <3% <3% <3% <3% <3%

The high value of MEK double rub test suggested that the coatings werechemically resistive. All the coating formulations, except thosecontaining IDA, had MEK double rubs above 400.

Based on König and pencil hardness, these coatings are considered to behard. As the degree of acrylation increases, the coatings were harder.Impact test data shows that the coatings are brittle, indicating highcrosslink density. Mandrel bend shows the flexibility of the filmcoatings. The lower cross-linking density of AESO and PAESSy 50 informulations with the monoacrylate diluents is suggested to be the causeof flexibility of those coatings.

Example 4 Anhydride Curing of Epoxidized Sucrose Esters

4.1 Materials.

Sucrose esters of fatty acids (SEFAs) were provided by Procter & GambleChemicals (Cincinnati, Ohio). They were the starting materials toprepare epoxidized sucrose esters of fatty acids (ESEFA). There are fourESEFAs used in this study. They are ESL (epoxidized sucrose linseedate),ESSF (epoxidized sucrose safflowerate), ESS (epoxidized sucrose soyate),and ESSB6 (epoxidized sucrose soyate B6). The epoxidized sucrose esterresins were prepared as in Example 1. Vikoflex 7170 epoxidized soybeanoil (ESO) was supplied by Arkema Inc. (Philadelphia, Pa.).4-methyl-1,2-cyclohexanedicarboxylic anhydride (mixture of isomers,98%), or hexahydro-4-methylphthalic anhydride (MHHPA), was purchasedfrom Alfa Aesar (Heysham, England). 1,8-diazabicyclo[5.4.0]undec-7-ene(≧99.0% GC) (DBU) was purchased from Sigma-Aldrich Co. (St. Louis, Mo.).

4.2 Epoxy-Anhydride Formulation and Curing

The equivalent ratio of epoxides to anhydrides was 1:0.5 or 1:0.75. DBUwas used at 1.5 wt % (based on the total weight of resins). The effectsof stoichiometric ratio on thermosetting properties were studied usingESL and ESSB6. In ESL anhydride curing, the equivalent ratios ofepoxides to anhydrides were used as 1:0.5, 1:0.4 and 1:0.3. In ESSB6anhydride curing, the equivalent ratios of epoxides to anhydrides wereused as 1:0.625, 1:0.5 and 1:0.4. As an example, the formulation of ESLanhydride curing in the equivalent ratio of epoxides to anhydrides of1:0.5 is as follows: 10 g of ESL (3.70 mmoles) containing 54.64 mmolesepoxides, was mixed with 4.60 g of MHHPA (27.35 mmoles) containing 27.35mmoles anhydride, in the presence of 0.219 g of DBU (1.44 mmoles).

ESEFA anhydride curing was done for 12 hours at 80° C., but ESOanhydride curing had to be done for 48 hours at 80° C. Coatings werecast on cleaned steel panels (QD panels from Q-panel) and glass panelsusing a draw-down bar with a gap of 8 mils. The thermosetting thin films(0.10-0.16 mm) on glass panels were carefully peeled off to make thespecimens for DMA and tensile testing. Thick thermosetting samples wereprepared by curing in Teflon molds, and their thicknesses werecontrolled in 1.6-2.0 mm.

4.3 Properties of the Cured Thermosets

The tensile properties of the cured thermosets are shown in Table 13.The modulus and tensile strength of the materials based on theepoxidized sucrose ester resins is significantly higher than that of thematerials based on epoxidized soybean oil. The materials based on ESOare highly elastomeric, as indicated by the high value of elongation atbreak, while the materials based on the epoxidized sucrose soyate resinsare much stiffer.

TABLE 13 The tensile properties of epoxy-anhydride thermosetting thinfilms in the equivalent ratio of epoxides to anhydrides of 1:0.5 TensileTensile Epoxy Modulus strength Elongation at toughness (J) × compounds(MPa) (MPa) break (%) 10³ ESL 1395 ± 191 45.8 ± 5.4 5.7 ± 2.6 8.44 ± 3.5ESSF  909 ± 179 31.5 ± 3.2 8.5 ± 2.7 11.5 ± 6.3 ESS 497 ± 38 20.3 ± 4.321.7 ± 7.8  29.4 ± 9.2 ESSB6 1002 ± 52  35.1 ± 3.6 5.4 ± 0.7  9.1 ± 3.8ESO  65 ± 10 10.2 ± 2.5 167 ± 19    97 ± 13.8 (Control)

Different stoichiometric ratios of epoxy to anhydride can also be usedto form the thermosetting materials. The properties of a series ofmaterials are shown in Table 14 and show that varying the stoichiometricratio can vary the properties of the materials.

TABLE 14 The tensile properties of epoxy-anhydride thermosetting thicksamples in the equivalent ratio of epoxides to anhydrides of 1:0.75 and1:0.5 Epoxide/ anhydride Tensile Epoxy (equivalent Modulus strengthElongation at compounds ratio) (MPa) (MPa) break (%) ESS 1:0.5  170.8 ±12.8 7.8 ± 0.4 11.0 ± 1.8 ESS 1:0.75 595.1 ± 8.2  21.8 ± 1.4   6.2 ± 1.0ESSB6 1:0.5  231.8 ± 40.5 8.9 ± 1.6 10.4 ± 2.2 ESSB6 1:0.75 643.9 ± 26.119.6 ± 5.7   4.5 ± 0.7 ESO (Control) 1:0.5   5.0 ± 0.16 1.2 ± 0.1 27.9 ±3.6 ESO (Control) 1:0.75  97.7 ± 28.7 6.0 ± 0.5 28.7 ± 5.6

The dynamic mechanical properties of the anhydride cured materials aregiven in Table 15. This data shows that the values of the glasstransition temperatures obtained from the anhydride curing of theepoxidized sucrose ester resins is significantly higher than thatobtained using ESO. In addition, the room temperature modulus alsodemonstrates that the ESE resins yield cured materials withsignificantly greater stiffness. The measured crosslink density (ve) inTable 13 also shows that the thermosets from the ESE resins issignificantly higher than that from ESO due to the higher degree ofepoxy functionality in the ESE resins.

TABLE 15 Dynamic mechanical properties and crosslink densities ofepoxy-anhydride thermosets Epoxide/ anhydride E′ E′ v_(e) Epoxy(equivalent T_(g) (MPa) at (MPa) at (×10³ mol/ compounds ratio) (° C.)20° C. T_(g) + 60° C. mm³) ESL 1:0.5 103.7 1,500 20.7 1.84 ESL 1:0.478.5 619 9.5 0.85 ESL 1:0.3 46.9 141 6.6 0.59 ESSF 1:0.5 71.3 1,103 7.70.69 ESS 1:0.5 48.4 103 5.6 0.50 ESSB6 1:0.5 79.6 368 13.8 1.23 ESO1:0.5 24.8 36 3.1 0.28 (Control)

Coatings were made from the anhydride curing of the ESE resins and thecontrol ESO and the data is shown in Table 16. As can be seen, thehardness of the coatings based on ESE resins is significantly higherthan the coatings based on ESO. Solvent resistance for the ESE coatingsis also significantly better than ESO.

TABLE 16 The properties of epoxy-anhydride coatings König Cross- MEKMandrel Epoxy Epoxide/ pendulum Pencil hatch double Reverse bend com-anhydride Thickness hardness hardness adhe- rub impact (elongation-pounds (Eq. ratio) (μm) (sec.) (gouge) sion resistance (in-lb) at-break)ESL 1:0.5 110 ± 7.0 183 H 4B >400 28 <2.5%  ESL 1:0.4  120 ± 17.7 90 F5B >400 >172 >28% ESL 1:0.4 94.4 ± 5.4  47 B 5B 330 >172 >28% ESSF 1:0.5113 ± 3.3 118 F 5B >400 32 4-4.5%  ESS 1:0.5 102 ± 8.4 63 2B 5B >40072 >28% ESSB6  1:0.625 99.8 ± 2.5  123 HB 3B >400 100 >28% ESSB6 1:0.5112 ± 4.5 115 B 5B >400 80 >28% ESSB6 1:0.4 99.5 ± 4.4  39 2B 2B320 >172 >28% ESO 1:0.5 108 ± 4.8 22 <EE 5B 25 >172 >28% (Control)

Example 5 Synthesis of Epoxidized Soyate Esters of Dipentaerythritol andTripentaerythritol

5.1 Materials:

Sucrose esters of soybean oil fatty acids, sucrose soyate, were providedby Procter & Gamble Chemicals (Cincinnati, Ohio). Acetic acid (ACSreagent, ≧99.7%), diethyl ether (ACS reagent, ≧99.0%), hydrogen peroxide(50 wt % solution in water), Amberlite IR-120H ion-exchange resin,sodium carbonate (ACS reagent), and anhydrous magnesium sulfate (reagentgrade, ≧97%) were purchased from Sigma-Aldrich, Inc. (St. Louis, Mo.).

Vikoflex 7170 epoxidized soybean oil was supplied by Arkema Inc.(Philadelphia, Pa.). RBD soybean oil was provided by Industrial Oils &Lubricants (Chicago, Ill.). BDH™ Methanol (ACS grade, ≧99.8%) waspurchased from VWR International (West Chester, P^(A)). Potassiumhydroxide (technical grade) was purchased from Mallinckrodt Baker, Inc.(Phillipsburg, N.J.). Dipentaerythritol (technical grade) andtripentaerythritol (technical grade) were purchased from Sigma-Aldrich,Inc. (St. Louis, Mo.). Dibutyltin oxide (98%) and dibutyltin dilaurate(95%) were purchased from Sigma-Aldrich, Inc. (St. Louis, Mo.). Allmaterials were used as received without further purification.

5.2 Synthesis of Fatty Acid Methyl Ester:

The synthesis of fatty acid methyl ester was carried out in a 500 mLfour-neck flask equipped with a mechanical stirrer, nitrogen inlet,thermocouple, and reflux condenser. 200 g of soybean oil (0.230 moles)was charged into the flask and was preheated to 65° C. with nitrogenpurge. 9.3 g of potassium hydroxide (0.166 moles) was dissolved into110.5 g of methanol (3.449 moles), and the solution was slowly chargedinto the flask to start the transesterification reaction. Themethanol/oil molar ratio was 15:1, and the catalyst concentration was3.2 wt % (based on the total weight of oil and methanol). The reactiontemperature was kept at 65±1° C. with methanol refluxing. The reactionwas allowed to run for 3 hours, and finally a transparent brownish redsolution was obtained. After it was cooled down to room temperature, thesolution was transferred into a separatory funnel. A large amount ofdistilled water was charged into the funnel, and the reaction mixturewas separated into two phases. The upper phase consisted of methylesters, and the lower phase contained the glycerol, monoglyceride,possible diglyceride, potassium hydroxide, and the excess of methanol.The upper methyl esters layer was successively purified with distilledwater until the water layer was clear. The residual water inside ofmethyl esters was eliminated by treatment with anhydrous magnesiumsulfate, followed by filtration. Finally, methyl esters were obtained asthe light yellow liquid. Usually, the yield of this FAME synthesis wasin the range of 65-70% due to the loss of monoglyceride in water.

5.3 Synthesis of Multi-Pentaerythritol Soyate:

The synthesis of multi-pentaerythritol soyate was carried out in a 250mL four-neck flask equipped with a mechanical stirrer, nitrogen inlet,thermocouple, condenser, and Dean-Stark trap. The degree of fatty acidsubstitution on multi-pentaerythritol was controlled by theFAME/multi-pentaerythritol molar ratio. Herein, the synthesis oftripentaerythritol soyate with full substitution was demonstrated as anexample. 25 g of tripentaerythritol (0.037 moles) and 157 g of FAME(0.537 moles) were charged into the flask and preheated to 225° C. withnitrogen purge. Dibutyltin dilaurate and dibutyltin oxide were used asthe organotin catalyst, and they were individually added in 0.05 wt %based on the total weight of tripentaerythritol and FAME. As thebyproduct of the transesterification, methanol was collected in theDean-Stark trap. The reaction was allowed to run for 7 hours, andfinally tripentaerythritol soyate was obtained as the yellow liquidresin.

5.4 Synthesis of Epoxidized Soyate Resins:

Epoxidation reactions were carried out in a 500 mL four-neck flask,equipped with a mechanical stirrer, nitrogen inlet, thermocouple andaddition funnel. Soyate resins were epoxidized using peracetic acidgenerated in situ from hydrogen peroxide and acetic acid, in thepresence of Amberlite IR 120H as catalyst. The molar ratio of aceticacid:hydrogen peroxide (H₂O₂):double bond was used in 0.5:2:1. Theproperties of the resins are shown in Table 17.

TABLE 17 Properties of resins before and after epoxidation IntrinsicDensity viscosity GPC (g/cm³) (100 ml/g), MW EEW Iodine Viscosity at 25°C. Mn difference Resin Epoxidation (g/eq.) value (mPa•s) 25° C. in THF(g/mol) (g/mol) PDI Soybean oil Cargill ™ — 136 79 0.920 1.10 1,290 291.10 ESO Vikoflex ™ 231 — 588 0.996 2.36 1,319 1.14 7170Dipentaerythritol Before — 124 341 0.939 2.92 2,353 130 1.26 soyate(DPS) After 268 1.25 1,192 1.000 3.27 2,483 1.28 TripentaerythritolBefore — 124 415 0.943 3.32 2,807 −35 1.15 soyate (TPS) After 261 1.361,368 1.001 3.58 2,772 1.18 Tripentaerythritol Before — 125 365 0.9462.98 2,349 156 1.11 soyate B6 (TPS After 270 1.05 1,824 1.011 3.21 2,5051.13 B6) Sucrose soyate Before — 117 425 0.945 2.41 2,379 252 1.08 (SS)After 248 0.44 2,160 1.017 3.15 2,631 1.08 Sucrose soyate Before — 115890 0.965 1.83 2,204 274 1.09 B6 (SS B6) After 256 0.73 5,460 1.036 2.942,478 1.20

Example 6 Coating Formulation and Properties

4-Methyl-1,2-cyclohexanedicarboxylic anhydride (mixture of isomers, 98%)(MHHPA) was purchased from Alfa Aesar (Heysham, England).Dodecenylsuccinic anhydride (mixture of isomers), and1,8-diazabicyclo[5.4.0]undec-7-ene (≧99.0% GC) (DBU) were purchased fromSigma-Aldrich Inc. (St. Louis, Mo.). Coatings were formulated at a 1:0.5ratio of epoxy to anhydride. Formulations were prepared as described inExample 4 and cured at 85° C. for 12 hours.

Properties of the coatings cured using MHHPA are shown in Table 18 andproperties for coatings cured using DDSA are shown in Table 19. Theproperties vary over a broad range depending on the structure of theepoxy resins, the curing agent used and the stoichiometric ratio.

TABLE 18 Properties of epoxy-anhydride coatings using MHHPA hardener(4-methyl-1,2- cyclohexanedicarboxylic anhydride) Epoxide/ Mandrelanhydride Pendulum Pencil Cross- MEK Impact Bending (molar Thicknesshardness, hardness hatch double (inch- (elongation- Epoxy ratio) (μm)sec (gouged) adhesion rubs lbs) at-break) ESO 1:0.5 108 ± 17 <EE 5B25 >172 >28% 4.8 EDPS 1:0.5 70.2 ± 37 EE 5B 55 >172 >28% 4.9 ETPS 1:0.585.1 ± 24 EE 5B 75 >172 >28% 5.1 ETPS_B6 1:0.5 93.6 ± 16 3B 5B 108148 >28% 7.6 ESS 1:0.5 102 ± 63 2B 5B >400 72 >28% 8.4 ESS_B6 1:0.5 112± 115 B 5B >400 80 >28% 4.5

TABLE 19 Properties of epoxy-anhydride coatings using DDSA hardener(dodecenylsuccinic anhydride) Epoxide/ Mandrel anhydride Pendulum PencilCross- MEK Impact Bending (molar Thickness hardness, hardness hatchdouble (inch- (elongation- Epoxy ratio) (μm) sec (gouged) adhesion rubslbs) at-break) ESO 1:0.5 89.4 ± 40 <EE 3B 87 160 >28% 7.5  1:0.75 79.3 ±22 <EE 4B 60 >172 >28% 4.3 EDPS 1:0.5 84.9 ± 40 5B 4B 238 120 >28% 9.2 1:0.75 80.2 ± 17 2B 5B 164 >172 >28% 8.3 ETPS 1:0.5 85.19 ± 22 4B 5B115 >172 >28% 10.7  1:0.75 96.6 ± 18 2B 5B 91 >172 >28% 8.5 ETPS_B61:0.5 102.2 ± 13 3B 5B 150 140 >28% 6.9  1:0.75 90.3 34 HB 4B 167128 >28% 9.3 ESS 1:0.5 97.6 ± 22 2B 5B 300 140 >28% 10.2  1:0.75 93.4 ±44 B 5B >400 >172 >28% 8.7 ESSB6 1:0.5 97.2 ± 56 F 5B 350 160 >28% 8.3 1:0.75 101.0 ± 92 F 5B >400 >172 >28% 7.4

Example 7 Polyols from Epoxidized Sucrose Soyate Resins and PolyurethaneCoatings

7.1 Raw Materials

Epoxidized sucrose soyate (ESS) and epoxidized sucrose soyate B6 (EssB6) were prepared from the epoxidation of the starting materials usingthe method in Example 1. As an amidine catalyst,1,8-diazabicyclo[5.4.0]undec-7-ene (≧99.0% GC) (DBU) was purchased fromSigma-Aldrich, Co. (St. Louis, Mo.). BDH™ Methanol (ACS grade, ≧99.8%)and 2-propanol (ACS grade, ≧99.5%) was purchased from VWR International(West Chester, Pa.). As an acid catalyst, tetrafluoroboric acid (48 wt %solution in water) was purchased from Sigma-Aldrich, Co. (St. Louis,Mo.). Tolonate IDT 70B (NCO equivalent weight=342 g/eq., 70% solids inbutylacetate), an aliphatic polyisocyanate based on isophoronediisocyanate trimer (IPDI homopolymer), was provided by Perstorp Group(Cranbury, N.J.). Desmodur N 3600 (NCO equivalent weight=183 g/eq.,solvent-free), an aliphatic polyisocyanate based on hexamethylenediisocyanate trimer (HDI homopolymer), was provided by BayerMaterialScience (Pittsburgh, Pa.). All materials were used as receivedwithout further purification.

7.2 Synthesis of Sucrose Soy-Based Polyols

7.2.1 Acid-Epoxy Reaction

Acetic acid, propionic acid, and 2-ethylhexanoic acid were individuallyused to react with ESS to produce sucrose soyate-based polyol, in thepresence of 1,8-diaza bicyclo[5.4.0]undec-7-ene (DBU) as catalyst. Thereactions were carried out at 125-130° C. Acid number titration was usedto monitor the reactions that would be stopped when acid number waslower than 15. Herein, 2-ethylhexanoic acid (EHA) was used as an exampleto synthesize polyol in the molar ratio of acid/epoxide as 0.8:1.Base-catalyzed acid-epoxy reaction was carried out in a 250 mLthree-neck flask, equipped with a mechanical stirrer, thermocouple andreflux condenser. 77.38 g of ESS (0.029 mol) containing 0.312 molepoxides and 35.99 g of EHA (0.250 mol) containing 0.250 mol carboxylicacid were added into the flask at room temperature. DBU catalyst wasused at 1 wt % of total weight of ESS and EHA. 1.13 g of DBU (0.007 mol)was charged into the flask. With a mechanical stirring, the mixture ofreactants and catalyst was heated to 130° C. After three and a quarterhours, the reaction was stopped with acid number as 12. A red-yellowhighly viscous liquid resin was obtained as the product. Since DBU canbe used as PU curing catalyst, there was no further purification afterreaction. Properties of the polyols are given in Table 20.

TABLE 20 Sucrose soyate-based polyols prepared with acid-epoxy reactionsAcid/ Reacted Epoxide Reaction Acid epoxides Hydroxyl Viscosity PolyolsAcid (molar ratio) time (hr) number (%) functionality (mPa•s) AA_1Acetic acid   1/1 11.0 52 72 8.6 38,000 AA_0.9 Acetic acid 0.9/1 6.5 3770 8.4 11,940 AA_0.6 Acetic acid 0.6/1 4.0 14 53 6.4 4,980 PA _0.6Propionic acid 0.6/1 5.5 15 52 6.2 12,160 EHA_0.9 2-ethylhexanoic 0.9/16.0 24 74 8.9 14,140 acid EHA_0.8 2-ethylhexanoic 0.8/1 3.25 12 72 8.615,100 acid EHA_0.6 2-ethylhexanoic 0.6/1 2.5 7.5 56 6.7 12,060 acidEHA_0.4 2-ethylhexanoic 0.4/1 0.5 1.0 40 4.8 5,060 acid

7.2.2 Alcohol-Epoxy Reaction

Both ESS and ESSB6 were used to study the epoxide hydroxylation inalcohol-epoxy reaction. Herein, ESS was used as an example in the molarratio of methanol/epoxide as 3:1. Acid-catalyzed alcohol-epoxy reactionwas carried out in a 500 mL four-neck flask, equipped with a mechanicalstirrer, thermocouple, reflux condenser and 250 mL addition funnel. 100g of ESS (0.037 mol) containing 0.403 mol epoxides dissolved into 150 mlof isopropanol and the solution was transferred into addition funnel.150 ml of isopropanol, 10 g of water, 40 g of methanol (1.25 mol), and 4g of tetrafluoroboric acid (48 wt % solution in water, 0.022 mol) werecharged into the flask and mixed well at room temperature. Once themixture in flask was heated to 45° C., ESS isopropanol solution startedto be dropwise added at a speed of 1 ml/min. The reaction temperaturewas controlled at 50° C. After the dropwise addition of ESS isopropanolsolution, the reaction was held at 50° C. for 20 minutes. 5 g of sodiumcarbonate (0.047 mol) was added to get rid of tetrafluoroboric acid. Theproduct solution was transferred into a beaker and dried with magnesiumsulfate anhydrous for overnight to remove water. The hydrated magnesiumsulfate was removed by filtration, and extra alcohols were removed bydistillation at reduced pressure. The polyols prepared are listed inTable 21.

TABLE 21 Sucrose soy-based polyols prepared with alcohol-epoxy reactionsHBF₄ (48 wt % in water)/ Dropwise Water/ speed Methanol/ Isopropanol/ESS of ESS epoxide methanol (weight solution Viscosity Polyols (molarratio) (ratio) ratio) (ml/min) (cPs) MESS_1 6/1 6/1 0.4/1/10 4.0 54,800MESS_2 3/1 6/1 0.4/1/10 1.0 31,600 MESSB6 3/1 6/1 0.4/1/10 1.0 185,000

7.3 Polyurethane Coating Formulations

Sucrose soyate-based polyols obtained from partially epoxide opening inacid-epoxy reactions were formulated with polyisocyanate in NCO/OHstoichiometric ratio as 1.1:1. In each formulation, 80% solids contentwas obtained in xylene solution. Sucrose soyate-based polyols obtainedfrom fully epoxide opening in alcohol-epoxy reactions were formulatedwith polyisocyanate in NCO/OH stoichiometric ratios of 1.1:1, 0.8:1, and0.6:1. In each formulation, 80% solids content was obtained in xylenesolution. PU coatings were cast on cleaned QD-36 steel panels and glasspanels using a draw-down bar with a gap of 8 mils. The coatings werekept at ambient for three hours. Tack free coatings were further curedin oven at 80° C. for one hour. PU coatings on steel panels were usedfor ASTM tests to evaluate coating properties. PU coatings on glasspanels were peeled off as thin films and used for DSC and DMAcharacterizations.

IDPI and HDI trimer are both aliphatic polyisocyanates. They were usedto react with sucrose soyate-based polyols to prepare PU coatings inthis study. The properties of PU coatings are shown in Table 22. Itshows that IPDI PU coatings have better hardness and solvent-resistance,and HDI PU coatings have better flexibility and better impact andbending resistance.

The stoichiometric ratio of acid to epoxide in the acid-epoxy reactionvaries the amount of hydroxyls available in the resulting polyol, whichconsequently affects the properties of the PU coatings. EHA producedpolyols (e.g. EHA_(—)0.4, EHA_(—)0.6, and EHA_(—)0.8) were cured by IPDItrimer in the same NCO/OH ratio. It shows that the higher amount ofhydroxyls provides a higher degree of crosslinking, which results in thecoating having better hardness and solvent resistance. Since theepoxides were fully reacted to generate hydroxyls in alcohol-epoxyreactions, the stoichiometry of NCO/OH in PU formulation was used tostudy its effect on the properties of coatings. It shows that the higherNCO/OH ratio results in PU coatings having better hardness and solventresistance, but weaker impact and bending resistance because of theirbrittleness.

TABLE 22 Properties of polyurethane coatings NCO/ König MEK Mandrel OHpendulum Pencil Cross- double Reverse bend Polyol Diisocyanate (molarThickness hardness hardness hatch rub impact (elongation- samples trimerratio) (μm) (s) (gouge) adhesion resistance (in-lb) at-break) EHA_0.8IPDI 1.1 75 ± 3.4 164 H 3B 215 80 >28% EHA_0.6 IPDI 1.1 71 ± 5.8 142 F3B 185 >172 >28% EHA_0.4 IPDI 1.1 89 ± 5.3 47 3B 5B 90 >172 >28% PA_0.6IPDI 1.1 84 ± 9.3 147 HB 1B 190 40 >28% AA_0.6 IPDI 1.1 66 ± 2.9 159 2H1B 240 40 <2.5%  AA_0.6 HDI 1.1 73 ± 6.2 10 5B 5B 130 >172 >28% MESS_2IPDI 1.1 70 ± 4.6 194 B 1B >400 <4 <2.5%  MESS_2 IPDI 0.8 67 ± 5.6 179 H4B 275 16 <2.5%  MESS_2 IPDI 0.6 66 ± 8.1 160 HB 4B 165 32 >28% MESSB6IPDI 1.1 71 ± 7.6 200 B 1B >400 <4 <2.5%  MESSB6 IPDI 0.8 87 ± 8.5 192HB 2B 350 <4 <2.5%  MESSB6 IPDI 0.6 67 ± 9.6 172 H 4B 270 <4 <2.5% MESS_2 HDI 1.1 79 ± 5.2 57 H 5B >400 8 >28% MESSB6 HDI 1.1 95 ± 6.8 141H 5B >400 32 >28%

The thermal and dynamic mechanical properties of PU coatings are shownin Table 23. Since DSC and DMA have different principles of measuringglass transition temperature (T_(g)), they will produce different T_(g)values for the same sample. But the trend of T_(g) with stoichiometry ineach measurement will be very similar.

For EHA produced polyols with different stoichiometry of acid/epoxide,the values of T_(g), E′ and v_(e) all increase with the increase ofacid/epoxide ratio. For MESS_(—)2 polyol cured with IPDI trimer indifferent stoichiometry of NCO/OH, the values of T_(g), E′ and v_(e) allincrease with the increase of NCO/OH ratio. PU thermoset prepared fromIPDI trimer always has higher value of T_(g), E′ and v_(e) than PUthermoset prepared from HDI trimer, in the same of NCO/OH ratio.

TABLE 23 Dynamic mechanical and thermal properties of polyurethane thinfilms DMA Polyol Diisocyanate NCO/OH DSC E′ (MPa) ν_(e) samples trimer(molar ratio) T_(g) (° C.) T_(g) (° C.) (@T_(g) + 60°) (×10³ mol/mm³)EHA_0.8 IPDI 1.1 101 127 11.8 1.05 EHA_0.6 IPDI 1.1 70 107 9.6 0.90EHA_0.4 IPDI 1.1 −16 17 2.1 0.25 PA_0.6 IPDI 1.1 72 115 8.6 0.79 AA_0.6IPDI 1.1 85 122 8.0 0.72 AA_0.6 HDI 1.1 9.8 6.4 6.7 0.82 MESS_2 IPDI 1.1141 118 7.1 0.65 MESS_2 IPDI 0.8 120 91 3.8 0.37 MESS_2 IPDI 0.6 101 863.6 0.35 MESSB6 IPDI 1.1 142 126 8.9 0.79 MESSB6 IPDI 0.8 134 123 7.50.67 MESSB6 IPDI 0.6 116 120 7.4 0.67 MESS_2 HDI 1.1 47 62 19.9 2.07MESSB6 HDI 1.1 64 80 21.5 2.14

1. An epoxy resin which is the reaction product of: a) a polyol having 4or more hydroxyl groups; and b) an ethylenically unsaturated fatty acid,optionally a saturated fatty acid, or mixtures thereof; and wherein atleast one ethylenically unsaturated group of the ethylenicallyunsaturated fatty acid is oxidized to an epoxy group.
 2. An epoxy resinof claim 1, wherein: a) the polyol having 4 or more hydroxyl groups isselected from pentaerithritol, di-trimethylolpropane,di-pentaerithritol, tri-pentaerithitol, sucrose, glucose, mannose,fructose, galactose, raffinose, copolymers of styrene and allyl alcohol,polyglycidol and poly(dimethylpropionic acid); and b) the ethylenicallyunsaturated fatty acid, optionally a saturated fatty acid, or mixturesthereof is a vegetable or seed oil.
 3. An epoxy resin of claim 2,wherein: a) the polyol having 4 or more hydroxyl groups is sucrose; andb) the vegetable or seed oil is selected from corn oil, castor oil,soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fattyacid, tung oil, vernonia oil, and mixtures thereof.
 4. An epoxy resin ofclaim 1 wherein the hydroxyls on the polyol are substantially esterifiedby the fatty acids b).
 5. An epoxy resin of claim 1 wherein a fractionof the hydroxyls on the polyol are esterified by the fatty acids b). 6.An epoxy resin of claim 1, wherein: a) the polyol having 4 or morehydroxyl groups is sucrose, and b) the ethylenically unsaturated fattyacid, optionally a saturated fatty acid, or mixtures thereof is soybeanoil.
 7. A curable coating composition comprising a) an epoxy resin ofclaim 1; and b) a cationic photoinitiator; and, c) optionally, one ormore diluents; and, d) optionally, one or more pigments.
 8. A coatingcomposition of claim 7, wherein: a) the polyol having 4 or more hydroxylgroups is sucrose, and b) the ethylenically unsaturated fatty acid,optionally a saturated fatty acid, or mixtures thereof is soybean oil.9. A coating composition of claim 7, wherein said coating composition iscured by contacting said coating composition with UV light.
 10. Anobject coated with the coating composition of claim
 7. 11. An epoxyresin composition made by converting the double bonds in a sucrose esterresin of a vegetable oil to epoxy groups.
 12. A method of making anepoxy resin comprising the steps of: a) esterifying a polyol having 4 ormore hydroxyl groups by reaction with a vegetable or seed oil containingan ethylenically unsaturated fatty acid and optionally a saturated fattyacid; and b) oxidizing at least one ethylenically unsaturated group ofthe ethylenically unsaturated fatty acid to an epoxy group.
 13. A methodof making an epoxy resin of claim 12, wherein: a) the polyol having 4 ormore hydroxyl groups is sucrose; and b) the vegetable or seed oil isselected from corn oil, castor oil, soybean oil, safflower oil,sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil,and mixtures thereof.
 14. An ethylenically unsaturated resin which isthe reaction product of an epoxy resin of claim 1 and an at least oneethylenically unsaturated acid.
 15. An ethylenically unsaturated resinof claim 14, wherein the ethylenically unsaturated acid is selected fromacrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaricacid, itaconic acid, and mixtures thereof.
 16. An ethylenicallyunsaturated resin of claim 14, wherein the ethylenically unsaturatedacid is acrylic acid or methacrylic acid.
 17. An ethylenicallyunsaturated resin of claim 14, wherein: a) the polyol having 4 or morehydroxyl groups is sucrose, and b) the ethylenically unsaturated fattyacid, optionally a saturated fatty acid, or mixtures thereof is soybeanoil.
 18. An ethylenically unsaturated resin of claim 16, wherein: a) thepolyol having 4 or more hydroxyl groups is sucrose, and b) theethylenically unsaturated fatty acid, optionally a saturated fatty acid,or mixtures thereof is soybean oil.
 19. A coating composition comprisinga resin of claim 14, an optional diluent, a free radical photoinitiator,and optionally, one or more pigments.
 20. A coating composition of claim19, wherein said coating composition is cured by contacting said coatingcomposition with UV light.
 21. An object coated with the coatingcomposition of claim
 19. 22. A method of making a resin havingethylenically unsaturated functionality comprising the steps of: a)esterifying a polyol having 4 or more hydroxyl groups by reaction with avegetable or seed oil containing an ethylenically unsaturated fatty acidand optionally a saturated fatty acid; b) oxidizing at least oneethylenically unsaturated group of the ethylenically unsaturated fattyacid to an epoxy group; and c) reacting at least a portion of the epoxygroups with an ethylenically unsaturated acid.
 23. A method of making aresin having ethylenically unsaturated functionality of claim 22,wherein: a) the polyol having 4 or more hydroxyl groups is sucrose; b)the vegetable or seed oil is selected from corn oil, castor oil, soybeanoil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid,tung oil, vernonia oil, and mixtures thereof; and c) the ethylenicallyunsaturated acid is acrylic acid or methacrylic acid.
 24. A resin havinghydroxyl functionality which is the reaction product of: an epoxy resinof claim 1, and at least one organic acid; or an epoxy resin of claim 1,and at least one alcohol.
 25. A resin of claim 24, wherein the resinhaving hydroxyl functionality is the reaction product of: the epoxyresin and an at least one organic acid selected from acetic acid,propionic acid, butyric acid, isobutyric acid, 2-ethylhexanoic acid, andmixtures thereof.
 26. A resin of claim 24, wherein the resin havinghydroxyl functionality is the reaction product of: the epoxy resin andan at least one alcohol selected from methanol, ethanol, n-propanol,n-butanol, isopropanol, isobutanol, 2-ethyl-1-hexanol, and mixturesthereof.
 27. A resin of claim 24, wherein: a) the polyol having 4 ormore hydroxyl groups is sucrose, and b) the ethylenically unsaturatedfatty acid, optionally a saturated fatty acid, or mixtures thereof issoybean oil.
 28. A thermoset coating composition comprising a resin ofclaim 24, a polyisocyanate, an optional solvent, an optional catalyst,and optionally, one or more pigments.
 29. An object coated with thethermoset coating composition of claim
 28. 30. A method of making aresin having hydroxyl functionality comprising the steps of: a)esterifying a polyol having 4 or more hydroxyl groups by reaction with avegetable or seed oil containing an ethylenically unsaturated fatty acidand optionally a saturated fatty acid; b) oxidizing at least oneethylenically unsaturated group of the ethylenically unsaturated fattyacid to an epoxy group; and c) reacting at least a portion of the epoxygroups with an organic acid or an alcohol.
 31. A method of making aresin having hydroxyl functionality of claim 30, wherein: a) the polyolhaving 4 or more hydroxyl groups is sucrose; and b) the vegetable orseed oil is selected from corn oil, castor oil, soybean oil, saffloweroil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernoniaoil, and mixtures thereof.
 32. An epoxy-anhydride composition comprisingan epoxy resin of claim 1, an acid anhydride, and a curing catalyst. 33.An epoxy-anhydride composition of claim 32, wherein in the epoxy resinthe polyol having 4 or more hydroxyl groups is sucrose, and theethylenically unsaturated fatty acid, optionally a saturated fatty acid,or mixtures thereof is soybean oil.
 34. An epoxy-anhydride compositionof claim 32, wherein the curing catalyst is a tertiary amine catalyst.35. A coating composition comprising an epoxy-anhydride composition ofclaim 24, an optional solvent, and optionally, one or more pigments. 36.An object coated with the coating composition of claim
 35. 37. Anepoxy-anhydride composition of claim 33, wherein the anhydride isselected from succinic anhydride, maleic anhydride,4-Methyl-1,2-cyclohexanedicarboxylic anhydride (MCHDA), dodecynylsuccinic anhydride, phthalic anhydride (PA), tetrahydrophthalicanhydride (THPA), hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (Me-THPA), methyl hexahydrophthalicanhydride (Me-HHPA), trialkyl tetrahydrophthalic anhydride (TATHPA),trimellitic anhydride, chlorendic anhydride, nadic methyl anhydride(methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride),pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride andmixtures thereof.